The role of confinement and corona crystallinity on the bending modulus of copolymer micelles measured directly by AFM flexural tests.

We present an approach which makes it possible to directly determine the bending modulus of single elongated block copolymer micelles. This is done by forming arrays of suspended micelles onto microfabricated substrates and by performing three-point bending flexural tests, using an atomic force microscope, on their suspended portions. By coupling the direct atomic force microscopy measurements with differential scanning calorimetry data, we show that the presence of a crystalline corona strongly increases the modulus of the copolymer elongated micelles. This large increase suggests that crystallites in the corona are larger and more uniformly oriented due to confinement effects. Our findings together with this hypothesis open new interesting avenues for the preparation of core-templated polymer fibres with enhanced mechanical properties.

In vivo biodistribution of stable spherical and filamentous micelles probed by high-sensitivity SPECT.

Understanding how nanoparticle properties such as size, morphology and rigidity influence their circulation time and biodistribution is essential for the development of nanomedicine therapies. Herein we assess the influence of morphology on cellular internalization, in vivo biodistribution and circulation time of nanocarriers using polystyrene-b-poly(ethylene oxide) micelles of spherical or elongated morphology. The glassy nature of polystyrene guarantees the morphological stability of the carriers in vivo and by encapsulating Indium-111 in their core, an assessment of the longitudinal in vivo biodistribution of the particles in healthy mice is performed with single photon emission computed tomography imaging. Our results show prolonged blood circulation, longer than 24 hours, for all micelle morphologies studied. Dynamics of micelle accumulation in the liver and other organs of the reticuloendothelial system show a size-dependent nature and late stage liver clearance is observed for the elongated morphology. Apparent contradictions between recent similar studies can be resolved by considering the effects of flexibility and degradation of the elongated micelles on their circulation time and biodistribution.

From chain collapse to new structures: spectroscopic properties of poly(3-thiophene acetic acid) upon binding by alkyl trimethylammonium bromide surfactants.

The binding of cationic surfactants with varying alkyl chain length to a regiorandom conjugated polyanion, poly(3-thiophene acetic acid) (PTAA), is studied in an aqueous buffer by using absorption and emission spectroscopies, photon correlation spectroscopy, isothermal titration calorimetry, and cryogenic transmission electron microscopy. We study the mixed solutions as a function of composition ratio R of surfactant molecules to monomer units molar concentrations, at low polymer concentration and in a very wide composition range (10(-6) < R < 10(2)) below the critical micellar concentration. Upon surfactant binding, the molecularly dispersed chains first collapse progressively and then form new structures as the mixed aggregates get enriched in surfactant. The collapse leads to a strong decrease of the conjugation length and to a blue shift of the absorption spectra by 30 to 50 nm. The new structures are responsible for a new intense emission band at about 600 nm, red-shifted by nearly 130 nm from the initial emission maximum of the polymer (~472 nm). As the surfactant tail becomes shorter, the blue shift of the absorption spectra and the intensity raise of the new emission are delayed to larger composition ratios while their variations become smoother functions of the surfactant concentration. These particular spectroscopic properties of PTAA seem related to its unique combination of a strongly hydrophobic backbone, a large ratio of contour length to persistence length, and an overall good aqueous solubility. Our results show that such features are well suited to design a colorimetric biosensor at small composition ratio, and a fluorescent biomarker at large composition ratio.

Diagram of the aging dynamics in laponite suspensions at low ionic strength.

We measure the dynamic structure factor (DSF) of probe particles embedded in an aging laponite suspension quenched by cessation of shear and the associated relaxation time tau as a function of wave vector q and aging time t(w). The different q dependences measured in the successive exponential and full aging regimes, respectively, tau approximately q(-2) and tau approximately q(-1.25), yield a weak positive q dependence for the aging time t(wc) corresponding to the crossover between the two regimes. This implies that the full aging behavior is first seen when investigating large length scales in the aging suspension. We propose a qualitative diagram of the aging dynamics and discuss the features of the DSF of the probes and of the matrix in the two aging regimes. Consistently with the idea that the full aging regime is first observed when probing large length scales, t(wc) is markedly shorter when the motion of the probes is tracked instead of the collective fluctuations of concentration in the matrix. The exponential aging regime is most probably related to the liquid-glass transition induced by the cessation of shear rather than to the aging of a glass.

Successive exponential and full aging regimes evidenced by tracer diffusion in a colloidal glass.

We study the aging of a colloidal laponite glass by measuring the dynamic structure factor of dilute embedded tracer particles on micrometric length scales. We show that an initial aging regime, where the decay time grows exponentially with aging time t(w), tau approximately exp (gamma t(w)), is followed by a full aging regime, tau approximately t(v)(w) with v approximately 1. The dynamics of the tracers is diffusive in the exponential regime and hyperdiffusive in the full aging regime, up to micrometric length scales.

Temperature-induced growth of wormlike copolymer micelles.

We study the temperature-induced growth of polymer micelles based on Pluronic P84 in brine (2 M NaCl) using small-angle neutron scattering, static and dynamic light scattering, and viscometry as a function of temperature and polymer concentration. Spherical micelles below 30 degrees C are shown to grow between about 30 and 40 degrees C into wormlike micelles long enough to enter the semidilute regime for polymer volume fraction larger than 0.005. The entanglements in this regime are responsible for a huge increase in the viscosity. Above about 41 degrees C, the micellar aggregates become denser as the cloud point is approached and the viscosity drops.